Abstract
The structural chemistry of a series of dpmaH (dpmaH = (dimethylphosphoryl)methanaminium) salts has been investigated using constructor graph representations to visualize structural dependencies, covering the majority of known dpmaH salts. It is shown that the structurally related α-aminomethylphosphinic acid can be integrated in the systematology of the dpmaH salts. Those dpmaH salts with counter anions that are weak hydrogen bond acceptors (ClO4−, SnCl62−, IrCl62−,I−) tend to form head-to-tail hydrogen bonded moieties purely consisting of dpmaH+ cations as the primarily structural motif. In structures with weak to very weak hydrogen bonds between the dpmaH+ cations and the counter anions, the anions fill the gaps in the structures. In salts with medium to strong hydrogen bond acceptor counter ions (Cl−, NO3−, PdCl42−), the predominant structural motif is a double head-to-tail hydrogen bonded (dpmaH+)2 dimer. These dimeric units form further NH···X hydrogen bonds to neighboring counter anions X, which results in one-dimensional and two-dimensional architectures.
Highlights
IntroductionNeutral (dimethylphosphoryl)methanamine (dpma) has been synthesized decades ago [1,2], and its crystal structure is well-known [3]
Neutralmethanamine has been synthesized decades ago [1,2], and its crystal structure is well-known [3]
In terms of the concepts of Crystal Engineering, the dpmaH+ is a building block with a threefold hydrogen donor functionality at one end and a hydrogen-bond acceptor functionality at the oxygen atom of the phosphoryl moiety at the other end (Scheme 1, left part). dpmaH+ can be abstracted by a block-shaped informative icon (Scheme 1, right part) which reduces the functionality of the tecton to the striking symbols of a blue plus sign and a red dot Crystals 2016, 6, 6; doi:10.3390/cryst6010006
Summary
Neutral (dimethylphosphoryl)methanamine (dpma) has been synthesized decades ago [1,2], and its crystal structure is well-known [3]. Infrequent use of constructor graphs may be related to the fact that the advantage of the abstraction of multifunctional molecules to dots is not intuitively comprehensible whereas the individual graph sets coding similar hydrogen-bond motifs are very handy for the description of one isolated structure or structure type. Further developments in this area concerns automated analysis and interpretation of hydrogen bonded networks [12]. A broader use of constructor graphs may support activities to systematize structurally and hierarchically related hydrogen bonded solids
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